Effects of bifenthrin on sex differentiation in Japanese Medaka (Oryzias latipes).

Bifenthrin (BF) is a pyrethroid insecticide used in urban and agricultural applications. Previous studies in early life stages of fish have indicated anti-estrogenic activity; however, estrogenic activity has been observed in adults. To test the hypothesis that BF impairs sex differentiation, larval Japanese Medaka were exposed to BF during a critical developmental window for phenotypic sexual differentiation. Fish were exposed to environmentally relevant concentrations of BF (0.15 µg/L and 1.5 µg/L), a single concentration (0.3 mg/L) of an estrogen receptor (ER) antagonist (ICI 182,780), and an ER agonist (0.2 ug/L) (17ß-estradiol). Fish were exposed at 8 days post hatch (dph) larvae for 30 days. Phenotypic sex, secondary sexual characteristics (SSC) and genotypic sex were investigated at sexual maturity (8 weeks). A trend towards masculinization (p = 0.06) based on the presence of papillary processes in anal fin rays of Japanese Medaka was observed in fish exposed to the lowest concentration of BF. However, genotypic gender ratios were not altered. These results show sex differentiation was not significantly altered by larval exposure to BF in Japanese medaka.

Fiproles in urban surface runoff: Understanding sources and causes of contamination.

Urban-use pesticides present a unique risk to non-target organisms in surface aquatic systems because impervious pavement facilitates runoff that may lead to serious contamination and ensuing aquatic toxicity. Fipronil is an insecticide used at high rates in urban environments, especially in regions such as California. This compound and its biologically active degradation products have been detected in urban runoff drainage and downstream surface water bodies at concentrations exceeding toxicity thresholds for sensitive aquatic invertebrates, necessitating a better understanding of the runoff sources and causes of this contamination at sites of application. In this study, we evaluated sorption of fipronil, fipronil desulfinyl, fipronil sulfide, and fipronil sulfone in urban dust, soil, and concrete, matrices commonly associated with the perimeter of a residential home. Samples were also collected from five single family homes treated with fipronil in Riverside, California, for five months to determine the occurrence of fipronil and its degradates in runoff water, urban dust, soil, and on concrete surfaces. Statistical analysis was performed to determine which urban matrices contributed more significantly to the contaminant levels in runoff water. Freundlich sorption coefficients for fipronil and its degradation products in dust were 3- to 9-fold greater than their values in soil. Fipronil and its degradates were detected in 100% of runoff samples and their presence was observed in dust, soil, and concrete wipe samples for 153 d after the treatment. Linear regression analysis showed that concrete surfaces were a primary source of all four compounds to runoff, and loose dust on concrete pavement also served as an important contributor. This study represents the first comprehensive investigation of the sources and causes for surface runoff contamination by fipronil and its degradation products. Findings highlight the importance to reduce fipronil residues on concrete surfaces through improved application methods and other mitigation practices.

Development of film-based passive samplers for in situ monitoring of trace levels of pyrethroids in sediment.

Residues of pyrethroid insecticides tend to accumulate in bed sediments due to their strong hydrophobicity. Rather than the total or bulk sediment concentration, it is the freely dissolved concentration (Cfree) that drives toxicity to benthic invertebrates. In this study we developed thin film-based samplers for in situ ambient monitoring of pyrethroids at trace levels in sediment. Out of five common polymer materials, polyethylene (PE) and silicone rubber (SR), were identified to offer superior enrichment for pyrethroids from sediment. To circumvent the slow equilibrium process, 13C-permethrin and bifenthrin-d5 were preloaded onto the films as performance reference compounds (PRCs). The PRC-preloaded film samplers were deployed at five sites in Southern California under field conditions for 7 d and retrieved for analysis. The sediment porewater Cfree of eight pyrethroids derived from PRC-PE films ranged from 173 to 903 ng/L, accounting for 18.2-36.1% of the corresponding total porewater concentrations. The PRC-SR film samplers yielded Cfree values closely mimicking those from the PRC-PE samplers, cross-validating the two sampling devices. Additionally, a significant positive association was found between the observed mortality from toxicity tests using Hyalella azteca and the Cfree of bifenthrin (r = 0.628, p = 0.02). A significant linear correlation (R2 = 0.99) between Cfree derived from in situ monitoring and that of ex situ measurement under equilibrium conditions was also observed. Results from this study demonstrated that the film-based samplers may be used for in situ ambient monitoring to detect biologically relevant contamination of pyrethroids in bed sediments, which may contribute to improved risk assessment for this class of widely used insecticides.

Effects of bifenthrin exposure on the estrogenic and dopaminergic pathways in zebrafish embryos and juveniles.

Bifenthrin is a pyrethroid insecticide used in urban and agricultural applications. Previous studies have shown that environmentally relevant (ng/L) concentrations of bifenthrin increased plasma concentrations of 17ß-estradiol (E2) and altered the expression of dopaminergic pathway components. The dopaminergic neurons can indirectly regulate E2 biosynthesis, suggesting that bifenthrin may disrupt the hypothalamic-pituitary-gonadal (HPG) axis. Because embryos do not have a complete HPG axis, the hypothesis that bifenthrin impairs dopamine regulation was tested in embryonic and 1-mo-old juvenile zebrafish (Danio rerio) with exposure to measured concentrations of 0.34 and 3.1 µg/L bifenthrin for 96 h. Quantitative reverse transcriptase polymerase chain reaction was used to investigate transcripts of tyrosine hydroxylase (TH), dopamine receptor 1 (DR1) and 2A (DR2A), dopamine active transporter (DAT), estrogen receptor α (ERα), ERß1, ERß2, luteinizing hormone ß (LHß), follicle-stimulating hormone ß (FSHß), vitellogenin (VTG), cytochrome P450 cyp19a1a, and cyp19a1b. Levels of E2 were measured by enzyme-linked immunosorbent assay (ELISA). Dopamine and its metabolites 3,4-dihydroxyphenylacetic acid (DOPAC) and homovanillic acid (HVA) concentrations were measured by liquid chromatrography-tandem mass spectrometry (LC-MS/MS). Significant decreases in TH and DR1 transcripts and HVA levels, as well as ratios of HVA/dopamine and HVA+DOPAC/dopamine, in zebrafish embryos were observed after bifenthrin treatment. In juveniles, a significant increase in the expression of ERß1 and the DOPAC to dopamine ratio was noted. These results show a possible antiestrogenic effect of bifenthrin in embryos, and estrogenicity in juveniles, indicating life-stage-dependent toxicity in developing fish. Environ Toxicol Chem 2018;37:236-246. © 2017 SETAC.

Development of polyurethane-based passive samplers for ambient monitoring of urban-use insecticides in water.

Widespread use of insecticides for the control of urban pests such as ants, termites, and spiders has resulted in contamination and toxicity in urban aquatic ecosystems in different regions of the world. Passive samplers are a convenient and integrative tool for in situ monitoring of trace contaminants in surface water. However, the performance of a passive sampler depends closely on its affinity for the target analytes, making passive samplers highly specific to the types of contaminants being monitored. The goal of this study was to develop a passive sampler compatible with a wide range of insecticides, including the strongly hydrophobic pyrethroids and the weakly hydrophobic fipronil and organophosphates. Of six candidate polymeric thin films, polyurethane film (PU) was identified to be the best at enriching the test compounds. The inclusion of stable isotope labeled analogs as performance reference compounds (PRCs) further allowed the use of PU film for pyrethroids under non-equilibrium conditions. The PU sampler was tested in a large aquarium with circulatory water flow, and also deployed at multiple sites in surface streams in southern California. The concentrations of pesticides derived from the PU sampler ranged from 0.5 to 18.5 ng/L, which were generally lower than the total chemical concentration measured by grab samples, suggesting that suspended particles and dissolved organic matter in water rendered them less available. The influence of suspended particles and dissolved organic matter on bioavailability was more pronounced for pyrethroids than for fipronils. The results show that the developed PU film sampler, when coupled with PRCs, may be used for rapid and sensitive in-situ monitoring of a wide range of insecticides in surface water.

Diclofenac in Arabidopsis cells: Rapid formation of conjugates.

Pharmaceutical and personal care products (PPCPs) are continuously introduced into the soil-plant system, through practices such as agronomic use of reclaimed water and biosolids containing these trace contaminants. Plants may accumulate PPCPs from soil, serving as a conduit for human exposure. Metabolism likely controls the final accumulation of PPCPs in plants, but is in general poorly understood for emerging contaminants. In this study, we used diclofenac as a model compound, and employed 14C tracing, and time-of-flight (TOF) and triple quadruple (QqQ) mass spectrometers to unravel its metabolism pathways in Arabidopsis thaliana cells. We further validated the primary metabolites in Arabidopsis seedlings. Diclofenac was quickly taken up into A. thaliana cells. Phase I metabolism involved hydroxylation and successive oxidation and cyclization reactions. However, Phase I metabolites did not accumulate appreciably; they were instead rapidly conjugated with sulfate, glucose, and glutamic acid through Phase II metabolism. In particular, diclofenac parent was directly conjugated with glutamic acid, with acyl-glutamatyl-diclofenac accounting for >70% of the extractable metabolites after 120-h incubation. In addition, at the end of incubation, >40% of the spiked diclofenac was in the non-extractable form, suggesting extensive sequestration into cell matter. The rapid formation of non-extractable residue and dominance of diclofenac-glutamate conjugate uncover previously unknown metabolism pathways for diclofenac. In particular, the rapid conjugation of parent highlights the need to consider conjugates of emerging contaminants in higher plants, and their biological activity and human health implications.

Distribution of pesticides in dust particles in urban environments.

In regions with a mild climate, pesticides are often used around homes for pest control. Recent monitoring studies have linked pesticide use in residential areas to aquatic toxicity in urban surface water ecosystems, and suggested dust particles on paved surfaces as an important source of pesticides. To test the hypothesis that dust on hard surfaces is a significant source of pesticides, we evaluated spatial and temporal patterns of current-use insecticides in Southern California, and further explored their distribution as a function of particle sizes. Pyrethroid insecticides were detected in dust from the driveway, curb gutter and street at 53.5-94.8%, with median concentrations of 1-46 ng g(-1). Pyrethroid residues were uniformly distributed in areas adjacent to a house, suggesting significant redistribution. The total levels of pyrethroids in dust significantly (p < 0.01) decreased from October to February, suggesting rainfalls as a major mechanism to move pesticide residues offsite. Fipronil as well as its degradation products, were detected at 50.6-75.5%, and spatial and temporal patterns of fipronil residues suggested rapid transformations of fipronil to its biologically active intermediates. Moreover, pyrethroids were found to be enriched in fine particles that have a higher mobility in runoff than coarse particles. Results from this study highlight the widespread occurrence of pesticides in outdoor dust around homes and the potential contribution to downstream surface water contamination via rain-induced runoff.

Practical Pest Management Strategies to Reduce Pesticide Runoff for Argentine Ant (Hymenoptera: Formicidae) Control.

The purpose of this study was to involve pest management professionals in the design of application techniques and strategies that would be efficacious and also reduce insecticide runoff. Our study involved measuring both the efficacy of treatments for the Argentine ant, Linepithema humile (Mayr), and the concurrent runoff of fipronil and pyrethroids. Two collaborating companies used low-impact protocols for controlling ants while minimizing runoff. Protocol 1 involved bimonthly treatments, while Protocol 2 was monthly. Both protocols involved an initial treatment with a fipronil spray around the foundation. At the garage door-driveway interface, the fipronil application was done as a pin stream for Protocol 1, and as a crack and crevice application in the expansion joint near the garage for Protocol 2. Protocol 1 replaced most pyrethroid sprays with bifenthrin granules placed around bushes and away from the driveway. For the next treatment on day 63, Protocol 1 also included cyfluthrin spray treatments around the house foundation and crack and crevice applications around the edge of the driveway. For the first treatment in Protocol 2, the fipronil spray was supplemented with spot treatments of cyfluthrin. For subsequent Protocol 2 treatments, botanical insecticides were applied. For weeks 1 and 2 posttreatment combined, Protocol 1 had significantly higher reductions in ant numbers compared with Protocol 2. Thereafter there were no significant differences between the protocols. Runoff of bifenthrin from the granules used with Protocol 1 was much lower than in previous trials involving bifenthrin sprays. Day 1 fipronil runoff for Protocol 2 was significantly lower than that for Protocol 1. This difference may be because of the crack and crevice application applied in Protocol 2. Cyfluthrin runoff was minimal for Protocol 2, which involved spot treatments to supplement the fipronil on day 1, or the botanical insecticides for subsequent treatments. Protocol 1 had a large peak of cyfluthrin runoff at day 63 corresponding to their house and driveway treatments.

Interlaboratory validation of the Mehlich 3 method as a universal extractant for plant nutrients.

The Mehlich 3 (M3) method is widely used to extract plant-available phosphorus from soil over a wide range of pH values. The method is also used by many laboratories to determine multiple plant-available nutrients simultaneously. However, except for P, this method has not been statistically validated within and among laboratories. The objective of this study was to determine the repeatability (within-laboratory performance) and reproducibility (among-laboratories performance) of the M3 method for several different nutrients by using a wide variety of soils. An in-house homogeneity test was conducted for 11 soils. Three replicates of each of the 11 soils were sent to 23 domestic and international laboratories for analyses primarily for K, Ca, Mg, Zn, Mn, Fe, and Cu. Samples were scooped, weighed, or both scooped and weighed for extraction. The various nutrients in the extracts were quantified by the participating laboratories by using inductively coupled plasma-atomic emission spectrometry. Ranges (in parentheses) of the repeatability relative standard deviation (RSDr) values for the scooped samples were K (3.88-6.14%), Ca (2.19-10.6%), Mg (2.27-5.73%), Zn (4.11-42.7%), Mn (3.15-8.53%), Fe (2.32-7.74%), and Cu (3.65-11.2%). For the weighed samples, the ranges (in parentheses) of the RSDr values were K (1.65-4.65%), Ca (1.43-16.9%), Mg (1.37-9.83%), Zn (2.60-33.0%), Mn (1.61-4.90%), Fe (1.56-4.47%), and Cu (2.95-17.9%). Ranges (in parentheses) of the reproducibility relative standard deviation (RSDR) values for the scooped samples were K (7.44-20.0%), Ca (7.10-33.5%), Mg (7.63-26.4%), Zn (11.6-48.7%), Mn (10.5-19.7%), Fe (12.4-22.0%), and Cu (8.86-45.3%). Ranges (in parentheses) of the RSDR values for the weighed samples were K (3.47-12.7%), Ca (7.61-34.6%), Mg (7.53-29.0%), Zn (10.6-49.2%), Mn (6.54-20.7%), Fe (11.0-21.5%), and Cu (9.73-43.0%). The Horwitz ratios (HorRat) were also used to evaluate the repeatability, HorRatr, and the reproducibility, HorRatR. Overall, the M3 method appears to be both repeatable and reproducible across the two categories for K, Mg, Zn, Mn, and Cu, and the vast majority of the HorRat values for both repeatability and reproducibility were within the acceptable range. However, a large number of soils in both the weighed and scooped categories displayed unacceptable HorRat values for the reproducibility of Ca and Fe, indicating that the M3 is not suitable for the extraction and quantitation of Ca and Fe in soils. The results of this study indicate that the M3 method for the determination of K, Mg, Zn, Mn, and Cu in soils is both accurate and precise when standardized procedures are used. The method has been proven to be suitable for use as a reference method for testing soil materials for extractable P, K, Mg, Zn, Mn, and Cu. Further study may be needed to confirm the suitability of the M3 method for Ca and Fe.